Reaction of diolefin polymers with hydrogen and carbon monoxide



Patented Mar. 6, 1951 UNITED REACTION OF DIOLEFIN POLYMERS WITH HYDROGENAND CARBON MONOXEDE Jean P. .liones and William Nelson Axe,Bartleaville, kla., assignors to Phillips Petroleum Company, acorporation of Delaware 7 No Drawing. Application May 6, i948,

Serial No. 25,523

12 Claims. (01.260-82) H 2 r l This invention relates to the preparationoi. polymerization of diolefins and by the copolyresinousoxygen-containing materials. In one aspect this invention relates topolyoleflnic polymeric hydrocarbons and their utilization in thepreparation of resinous oxygen-containing compounds. In a more specificaspect this invention relates to the utilization of clay tower polymersfor the production of resinous oxygen-containing compounds. 1

Cracking of unrefined distillates is a common cracked product of such astep contains polyolefinic compounds which have potential gumforming andcolor-forming properties and are detrimental, therefore, to the use ofthe distillates in finished stocks. A widely used process for theremoval of such polyolefinic compounds is a clay treatment process inwhich a normally liquid, cracked distillate stream having an end point01. about 410 to 450 F. is contacted with an absorptive clay, and theaforesaid polyolefin compounds contained therein are selectivelypolymerized and subsequently removed as polymeric by-products. Thepolymeric by-products, so produced are utilized in the process of thisinvention and are commonly referred to as clay tower polymers"; they areproducts ofhomopolymerization of polyolefins and of copolymerization ofpolyolefins with monoolefins and/orother polyolefins, and in any caseare more highly unsaturated than mono-.

Monoolefijs contained in the distillate olefins. being treated arepolymerized in very minor amounts during th clay treatment.

Although the clay treating process can be conducted in the vapbr, liquidor mixed phase, the mixed phase is pi eferable since such conditionsminimize the loss; of monooleflns. Temperature conditions of the [claytreating process are generally in the range of from 250 to 750 F. andthe pressure is min 50 to 600 p. s. 1. The total clay merization oidiolefins and monoolefins.

tower polymer by-"product occurs usually as a. normally viscous liquidmaterial; it chiefly comprises polyolefinic polymeric compounds in themolecular weight range of 200 to 800. The normally solid fractions theeof comprise polyoleflnic polymers having molecular weights as high asfrom 500 to 800, although the major proportion of such solid fractionsis in the molecular weight range of 300 to 500. The liquid fractionschiefly comprise polymeric materials formed by the hemp The generalproperties of clay tower polymers are shown in the following tabulation:

Normally Total (lay Solid Fraclower tions of Polymer Clay Tower PolymerGravit API F 1040 Nonvo stile Content, per cent l 60-90 1 Iodine Number1 190-250 i-300 Viscosity F., SUS B i Viscosity (I) 200 F., BUS FlashPoint. Ffi Fire Point, F. Pour Point. F. Soitening Point 5 1 Per centnonvoiatiles as measured at 225 F. for a duration of 3 v i' i is-g-ramsiodine that will react with 100 grams of sample.

ASTM designation 446-39.

' ASTM designation D9245.

l AS'TM designation D-97.

ASTM designation D36-26. 7

Although a clay treating process as above de scribed, is a preferredsource of polyolefinic polymeric hydrocarbons for the accomplishment ofthe objects of this invention, other sources may be utilized therefor.For example, conjugated polyolefinic hydrocarbons such as butadiene,pentadiene, cyclopentadiene, hexadiene, and the like, may be polymerizedby any of various known polymerization methods, to produce polyolefinicpolymeric hydrocarbons, suitable in the practice of our invention. Suchpolyolefinic compounds, as above named, can also be copolymerized withmonooleflnic hydrocarbons to form polyoleflnic polymeric hydrocarbonsadvantageously employed in our invention.

,An object of this invention is to provide a method for the preparationof resinous oxygencontaining materials.

Another object is to provide a method for the utilization of clay towerpolymers to produce resinous oxygen-containing materials.

A further object is to convert normally liquid or solid polymerichydrocarbons having greater unsaturation than monoolefins to resinousoxygen-containing materials.

Other objects will be apparent, to one skilled in the art, in the lightof the accompanying disclosure and discussion.

In accordance with this invention a polymeric hydrocarbon havingv agreater degree of unsaturation than a monoolefln and having a molecularweight in the range of 200 to 800, is reacted with carbon monoxide andhydrogen in the presence of a suitable Fischer-Tropsch catalyst to forma resinous, solid oxygen-containing product. The

. reaction is preferably conducted in two steps.

In the first step, the polymeric starting material is reacted withhydrogen and carbon monoxide to form a resinous product, and in thesecond step the resinousproduct so formed is further reacted withhydrogen in the absence of carbon monoxide, either in the presence ofthe original catalyst or of a suitable hydrogenating catalystsubstituted therefor. The product of the second step is generally aclear, solid oxygen-containing resinous material especially suitable foruse as a coating material. I

Polymeric hydrocarbons utilized in the process of this invention areclay tower polymers, or any fraction or fractions thereof, and thoseproduced by polymerizing a low-boiling diolefin, as butadiene or itshomologues alone, or in the presence of a monoolefinic hydrocarbon suchas isobutylene or styrene or homologues of either.

We prefer to conduct our process in two steps as aforesaid. However,depending upon the particular reactants and reaction conditionsselected, we may obtain a valuable solid resinous material asv a productof the first reaction step. In a large number of instances, however, thepreferred resinous material is obtained as a product of the combinedfirst and second reaction steps.

When we utilize liquid polymeric hydrocarbons, we prefer in mostinstances to employ an inert diluentsuch as hexane, cyclohexane,heptane, and the like. Such a diluent serves as a medium for the entirereaction and contains the catalyst in a finely divided suspended state.When utilizing normally solid polymeric materials a solvent, such as aninert diluent of the type above described is advantageously employed asa reaction medium even though in most instances, such a solid polymericmaterial is a liquid at the reaction temperature.

In the practice of a preferred form of our invention, we dissolve thehydrocarbon reactant in an inert diluent, such as normal hexane orcyclohexane, in an amount usually within the limits of 30 to 90 per centby weight; lower concentrations of the hydrocarbon reactant in thesolution may be employed, if desired. A Fischer-Tropsch catalyst, i. e.,a material which serves as a catalyst in the hydrogenation of carbonoxides, is suspended in a finely divided state in the solution abovedescribed, in an amount in the range of from 1 to per cent by weight.Water gas, 1. e., a mixture of hydrogen and carbon monoxide, containinghydrogen in molar ratio to carbon monoxide within the limits of 0.1:1 to2:1, is added to the solution at a pressure within the range of 50 to4500 p. s. 1.; more preferably in the range of 500-2000 p. s. i.Hydrogen and carbon monoxide reactants may be added to the reactionsolution separately, if desired. The reaction is then carried out inafirst step in a temperature range of from 100 to 400 F., and a contacttime of at least 10, minutes; more often the time is at least in therange of from 30 to 90 minutes and may be as high as 10 hours. Theproduct from the first step, is usually a mixture of saturated andunsaturated resinous oxygen containing materials having utility asdrying oils and coatings. However, we prefer usually to further reactthe above mentioned product with hydrogen in a second step. This isdone, subsequent to removal of carbon monoxide from the system andreplacement of same with hydrogen. We may do this by releasing thepressure in the system, purging the system preferably with hydrogen, andthen adding hydrogen thereto at about the same pressure employed in thefirst reaction step. The second step is then carried out under about thesame conditions of temperature, pressure, catalyst, and contact time asthose of the first step, although, in some cases, it is desirable to usesomewhat higher pressures. No other change in reaction conditions needbe eifected to make the hydrogenation substantially complete. The chiefproduct of the second reaction step is a celar, solid oxygen-containingresinous material and is especially suitable as a coating material andas an ingredient for varnishes, lacquers, and the like.

In the second step it may be, in some instances, desirable to substitutea different hydrogenation catalyst for the original catalyst. This isespecially advantageous from an economical standpoint in cases where thecost of the original catalyst is relatively high as compared to that ofthe hydrogenation catalyst. Another advantage to be gained thereby is inthe treatment of sulfurcontaining stocks wherein a hydrogenationcatalyst uninhibited by the presence of sulfur would be required.

Our process offer especial utility in its application to clay towerpolymers as a starting material. The characteristics of clay towerpolymers have long been known and the polymers long been considered tobe of no special value. In many cases, clay tower polymers as aby-product of the clay-treating process have presented difl'icultdisposal problems. By the application of our process, by-product claytower polymers are converted to valuable resinous oxygen-containingcompounds.

Our process has further utility as regards its application to clay towerpolymers, in view of their constantly changing composition which isdependent upon the specific hydrocarbon feed being processed and theconditions necessary to effect the required clay treatment. Our processoffers a high degree of utilization of such by-product polymersthroughout their entire range of composition.

Our preferred Fischer-Tropsch catalyst is a cobalt-thoria catalystsupported on kieselguhr and contains the three components in arespective weight ratio of about :18z100. Other ratios may be employedif desired. However, the use of other Fischer-Tropsch catalysts such asiron and/or nickel, is applicable to our process. All such catalysts maybe supplemented when desired, withone or more promoters or modifierssuch as, oxides of alkali and alkaline earth metals.

We prefer to apply our process to sulfur-free stocks. In many instancesthis would be achieved by desulfurization of our feed stocks. As regardsthe utilization of sulfur-containing clay tower polymers, sulfur-freestocks would be most easily procured by desulfurization of the crackedhydrocarbon fraction to be clay-treated by desulfurizing the charge tothe initial cracking step, or by the clay treatment of stocks initiallysulfur-free. However, we can utilize sulfur-containing feed stock in thefirst step of our process, if desired, when we employ a cobalt catalystsuch as the one above described. In the second step, we maysubstitute-for the cobalt catalyst a hydrogenation catalyst having anactivity unimpaired by the presence ofsulfur-containing materials. Sucha well-known catalyst is molybdenum sulfide.

Advantages of this invention are illustrated by the following examples.The reactants and their proportions and other specific ingredients arepresented as being typical and should not be construed to limit theinvention unduly.

Example 1 Tea reaction bomb is added a viscous liquid clay tower polymerhaving a solids content of 85 per cent an API gravity of 15.7", a flashpoint of 220 F., a viscosity of 210 F. of 37 SUS, a pour point of '-5F., and an iodine number of 224. The polymeric charge material isdissolved in cyclohexane in a weight ratio thereto of 1:2,

and 5 per cent of a finely divided Flscher-Tropsch catalyst comprisingcobalt, thoria, and kieselguhr in a respective weight ratio of100:18z100 is suspended in the solution. An equimolar mixture ofhydrogen and carbon monoxide is added to the reaction bomb at a pressureof 500 p. s. i. The contents of the bomb are agitated while bringing itto a temperature level of 300 F. which is maintained thereafter for 30minutes. The reaction mixture is then cooled and the gases released.

The system is then purged with hydrogen to remove the last traces ofcarbon monoxide, after which hydrogen is added at a pressure of about500 p. s. i. and the bomb contents agitated and heated as abovedescribed for another 30 minute reaction period. After the bomb iscooled, the resulting reaction products are recovered. The chief productcomprises a clear, normally solid resinous, oxygen-containing materialhaving properties especially suiting it for use in paints and lacquers.

Example II A normally solid fraction of a clay tower polymer having asolids content of 100 per cent as measured at 225 F. for a period of 3hours, an iodine number of 220, and a softening point of 178 F. isdissolved in normal hexane in a weight ratio thereto of 1:2, and 8 percent of a finely divided Fischer-Tropsch catalyst comprising cobalt andthoria on kieselguhr in a respective weight ratio of 100:182100 issuspended in the solution. An equimolar mixture of hydrogen and carbonmonoxide is added to the reaction system at a pressure of 1000 p. s. i.The reaction mixture is agitated and heated to a temperature of 400 F.The reaction conditions are maintained for minutes and the reactionmixture subsequently cooled. The gases are released from the cooledmixture and the system subsequently purged with hydrogen to remove thelast traces of the carbon monoxide. The cobalt catalyst is removed fromthe reaction system and is replaced with a hydrogenation catalystcomprising molybdenum disulfide. The system is purged with hydrogenafter which hydrogen is added at a pressure of about 1000 p. s. i. andthe reaction mixture agitated and again heated for a period asaioredescribed. After the bomb is cooled, the resulting reactionproducts are recovered. The chief product comprises a clear, normallysolid resinous oxygen-containing material which is quite stable and isespecially suited for use as a coating and as an ingredient in paintsand lacquers.

Example III Butadiene was polymerized and the polymer product reactedwith carbon monoxide and hydrogen to produce a clear, dark, solid,resinous,

. stirred stainless steel reactor along with 0.016 lb.

sodium, as a 20 per cent dispersion in xylene. About 1.60 lbs. ofbutadiene wa then gradually added to the reactor contents at aconstantly maintained pressure of 30 p. s. i. g. and at a temperature ofabout 158 F. The reaction time was about 5 hours. Solid catalyst andminor amounts of solid polymer were removed from the total reactionmixture by filtration. The liquid eilluent was water washed anddebenzenized and dexylenized at a temperature of 212 F. under reducedpressure. The resulting polymeric product was a reddish, viscoushydrocarbon material having a molecular weight in the range of from 400to 2000, and was pentane soluble. Polybutadiene produced in this mannerhas a viscosity within the range of 40 to 50 SAE, which range is withinthe broader range of 200 to 11,000 SUS as measured at 100 F., disclosedhereinabove in defining the clay tower polymer reactant materials, ofour process.

About 84 grams of the pentane-soluble material was diluted with 100 ml.of n-heptane and charged to a 300 ml. reactor. About 6.5 grams ofcobalt-thoriakieselguhr catalyst (100 18: 100) previously reduced withhydrogen for 24 hours at a temperature of 752 F., wa added to the 300ml. reactor. The reactor was then charged with an equimolar mixtureofoarbon monoxide and hydrogen to a pressure of 2000 p. s. i. Agitationof the reaction mixture was maintained during the entire initial heatingperiod. The pressure slowly increased with increased temperature untilreaction occurred as indicated by a decrease in reaction pressure. Thetemperature was thereafter maintained at a substantially constant level,and additional gas mixture was charged to maintain the pressure level at2000 p. s. i. After a 5 hour reaction period at a temperature of 350 F.and a pressure of 2000 p. s. i. g., heating was discontinued and thereactants were permitted to cool. The reaction system was depressuredand a sticky, black, fiuify solid was recovered. All the n-heptane wasdissolved or occluded in the solid catalyst and product mixture. Thetotal solid product wa removed and the reactor was conditioned for asubsequent step, hereinafter described. About one-half of the totalsolid product of the carbon monoxide-hydrogen reaction was subjected toextraction with boiling benzene. About 30 per cent of the total productwas benzene soluble and the remaining 70 per cent was found to beinorganic. Resinous extract material, comprising the product of thereaction was clear brown in color, and rapidly hardened upon standing inair. After two days standing the material became virtualy insoluble inbenzene. Benzene solutions of these resins, when applied on glass,formed a hard, dry film immediately upon evaporation of the solvent. Ina subsequent reaction step the remaining portion of the total solidproduct of the carbon monoxide-hydrogen reaction was admixed with moren-heptane and the admixture, together with 6.3grams of a copbariumnitrate and ammonia. A precipitate thus formed was filtered, washed anddried. The dried precipitate, orange colored, was pulverized and thenslowly decomposed over a flame. During the decomposition the color ofthe precipitate gradually changed from orange to brown and finally toblack. The black decomposition product was cooled and bleachedwithdilute acetic acid (about per cent), filtered washed, dried andpulverized. The catalyst thus prepared comprises the copper chromitecatalyst referred to herein.

Hydrogen was charged to the n-heptane-resincatalyst mixture to apressure of 2000 p. s. i. Heat was applied and initial reaction wasobserved at a temperature of 390 F. Slight pressure decreases occurredover a 4 hour period while maintaining a temperature level of 390 F.After the 4 hour period, heating was terminated and the reactantscooled. The total hydrogenated product was subjected to benzeneextraction in a manner identical to that described above for product ofthe carbon monoxide-hydrogen reaction. The total solid product contained46 per cent by weight of benzene soluble resin, which was tach and darkbrown in color and which did not harden in the presence of air over a 24hour period at room temperature.

As will be evident to those skilled in the art,

various modifications can be made or followed, in the light of theforegoing disclosure and discussion, without departing from the spiritor scope of the disclosure or from the scope of the claims.

We claim:

1. A process for the preparation of a resinous oxygen-containingmaterial from a polymer of a conjugated diolefln containing from 4 to 6carbon atoms in the molecule, having a viscosity within the limits of200 and 11,000 SUS as measured at 100 F. and having a molecular weightwithin the limits of 200 and 2,000, comprising reacting such a polymerwith hydrogen and carbon monoxide in the presence of a catalyst activein the hydrogenation of carbon monoxide with hydrogen for a contact time01' at least 10 minutes, at a temperature within the limits of 100 and400 F., and at a pressure within the limits of 50 and 4500 p. s. l., andrecovering a resinous oxygen-containing material from the reactionmixture as a product of the process.

2. A process for preparing a resinous oxygencontaining material from apolymer of a conjugated diolefln containing from 4 to 6 carbon atoms inthe molecule, having a viscosity within the limits of 200 and 11,000 SUSas measured at 100 F. and having a molecular weight within the range of200 to 800,. comprising reacting in a first step such a polymer withhydrogen and carbon monoxide in the presence of a cobalt-containingcatalyst active in the hydrogenation of carbon monoxide with hydrogenfor a contact *time of at least 10 minutes at a temperature in the rangeof 100 to 400 F., at a pressure within the limits of 50 and 4500 p. s.i.; in a second reaction step removing carbon monoxide and said catalystfrom the reaction system above described, replacing the carbon monoxideso removed with hydrogen, replacing said catalyst 3. A process for thepreparation of a solid oxygen-containing resinous material from apolybutadiene havinga molecular weight in the range of 400 to 2000 and aviscosity within the limits of 40 and 50 SAE: reacting saidpolybutadiene with water gas at a temperature in the range of 100 to 400F., and at a pressure in the range 0150 to 4500 p. s. i. for a contacttime of at least 10 minutes in the presence of a cobalt-thoria catalystsupported on kieselguhr; said water gas containing hydrogen to'carbonmonoxide in a mol ratio within the limits of 0.1:1 to 2:1, andrecovering from the reaction mixture a glassy, resinousoxygen-containing solid.

4. A process for the preparation of an oxygencontaining resinousmaterial from a polybutadiene having a molecular weight in the range of400 to 2000 and a viscosity in the range of 40 and 50 SAE, in a firststep reacting said polybutadiene with water gas in the presence or acobalt-containing catalyst active in the hydrogenation of carbonmonoxide with hydrogen, at a temperature in the range of 100 to 400 F.and at a pressure in the range of 50 to 4500 p. s. i. for a contact timeof at least 10 minutes; said water gas containing hydrogen in a molratio to carbon monoxide within the limits of 0.1:1 to 20:1; in a secondreaction step removing carbon monoxide from the reaction mixture abovedescribed and replacing same with hydrogen, maintaining aforesaidconditions of temperature, pressure, contact time, and catalyst, andrecoveringfrom the reaction mixture of said second step a tacky resinousmaterial.

5. A process for preparing a resinous oxygencontaining material from apolymer of a conjugated diolefin containing from 4 to 6 carbon atoms inthe molecule and having a viscosity within the limits of 200 to 11,000SUS as measured at 100 F., comprising reacting in a first step such apolymer having a molecular weight within the limits of 200 to 800,dissolved in an inert dilrent in a proportion therein in the range of 30to weight per cent, with hydrogen and carbon monoxide in the presence ofa cobalt catalyst containing a metal oxide activator and active in thehydrogenation or carbon monoxide with hydrogen, for a duration of atleast 10 minutes, at a temperature on the range of -400 F., and at apressure within the limits of 50 to 4500 p. s. 1.; in a second stepremoving carbon monoxide from the reaction mixture above described andreplacing same with hydrogen, maintaining aforesaid conditions oftemperature, pressure, duration, and catalyst, and recovering from thereaction mixture of said second step a resinous oxygen-containingmaterial.

6. The process of claim 1 wherein the polymer starting materialcomprises a product of the copolymerization of a monolefinic hydrocarbonand a diolefln.

7. A process for the production of a resinous I oxygen-containingmaterial from a normally with a hydrogenation catalyst selected from thegroup consisting of copper chromite, molybdenum sulfide and molybdenumoxide, maintaining the aforesaid conditions of temperature, pressure andcontact time, and recovering from the reaction mixture of said secondstep a resinous oxygen-containing product.

solid polymer by-product of a mixed phase clay treatment of unrefinedcracked distillate conducted in the presence of a contact masscomprising a clay, at a temperature in the range of 250 to 750 F. and ata pressure in the range of 50 to 600 p. s. i.; said polymer by-productconsisting of 100 per cent nonvolatile material as measured for aduration of 3 hours at a temperature of 225 F., having an iodine numberin the range of 190 to 300, and a softening point within the limits ofto 200 F.; said process comprising dissolving said normally solidfraction in "atsasos an inert diluent to comprise .irom 30 to 90 percent by weight of the solution, reacting in a first step said dissolvedfraction with water gas in the presence 01 a cobalt-containing catalystactive in the hydrogenation of carbon monoxide with hydrogen suspendedin said solution in a proportion therein of from 1 to per cent byweight, at a temperature in the range of 100 to 400F., a pressure in therange of 50 to 4000 p. s. i., and for a contact time of at least 10minutes; said water gas containing hydrogen in a mol ratio to carbonmonoxide in the range of 0.1 to 2.0; in a second step removing carbonmonoxide from the reaction mixture above described and replacing samewith hydrogen, maintaining aforesaid conditions of duration,temperature, pressure, and catalyst, and recovering from the reactionmixture of said second step a resinous oxygen-containing material.

8. A process for the production of a resinous oxygen-containing materialfrom the total polymer by-product of a mixed phase clay treatment ofunrefined cracked gasoline conducted in the presence of a contact masscomprising a clay at a temperature in the range or 250 to 750 F., and apressure in the range of 50 to 600 p. s. 1.; said total polymer havingan API gravity in the range of 10 to 40, a nonvolatiles content in therange of 60 to 90 per cent by weight, an iodine number in the range of190 to 250, a viscosity at 200 F1 in the range of 40 to 150 SUS, a flashpoint in the range of 185 to 325 F. a tire point in the range of 205 to345 F., and a pour point in the range of --20 to 60 F., said processcomprising in a first step dissolving said total product in an inertdiluent to comprise from 30 to 90 per cent by weight of the solution,reacting said dissolved product with water gas in the presence of acatalyst containing cobalt and active in the hydrogenation of carbonmonoxide with hydrogen, suspended in said solution in a proportiontherein irom 1 to 10 per cent by weight, at a temperature in the rangeof 100 to 400 F., a pressure in the range or 50 to 4500 p. s. i., andfor a duration of at least 10 minutes; said water gas containinghydrogen in a mol ratio to carbon monoxide in the range of 0.1 to 2.0;in a second step removing carbon monoxide from the reaction mixtureabove described and replacing same with hydrogen, maintaining aforesaidconditions of duration, temperature, pressure, and catalyst, andrecovering from the reaction mixture of said second step a resinousoxygen-containing material.

9. The process of claim 1 wherein said catalyst is an iron-containingcatalyst.

10. The process of claim 1 wherein said catalyst is a nickel-containingcatalyst.

11. A process for preparing a resinous oxygencontaining material from apolybutadiene having a molecular weight in the range of 400 to 2000 anda viscosity in the range of 40 to 50 BAE, in a first step reacting saidpolybutadiene with hydrogen and carbon monoxide in the presence of acatalyst active in the hydrogenation of carbon monoxide with hydrogen,for a contact time of at least ten minutes, at a temperature in therange 01 to 400 F. and at a pressure within the limitation of 50 to 4500p. s. i. g.; in a second reaction step removing carbon monoxide and thecatalyst or said first step from the reaction mixture, replacing saidcarbon monoxide with hydrogen and replacing the catalyst thus removedwith copper chromite as a hydrogenation catalyst,

maintaining the aforesaid conditions of contact time, temperature, andpressure, and recovering from the reaction mixture 01' said second ate aresinous oxygen-containing material. 12. A method for preparing aresinous oxygencontaining material from a polymer of a con-.

iugated diolefln containing from 4 to 6 carbon atoms in the molecule andhaving a viscosity within the limits of 200 to 11,000 SUS as measured at100 Fr having a molecular weight in the range of 200-2000, comprisingreacting such a polymer with hydrogen and carbon monoxide for a contacttime of at least 10 minutes, at a temperature in the range of 100-400 F.and a pressure within the limits 01 50 to 4500 p. s. i. g., in thepresence of a catalyst active in the hydrogenation of carbon monoxidewith hydrogen and containing cobalt, thoria, and kieselguhr, in arespective weight ratio 0! 100:18:100; and recovering from the totalreaction mixture a resinous v oxygen-containing material.

JEAN P. JONES.

WILLIAM NELSON AXE. I

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Wender et al., Bureau of Mines RI. 4270, June1948, 26 pages, especially pages 8 and 9.

Certificate of Correction v Patent 'No. 2,544,555 March 6, 1951 JEAN P.JONES ET AL.

It is hereb certified that error appears in the printed specification ofthe above numbere patent requiring correction as follows:

Column 4, line 17, for celar read clear; column 6, line 7 4, after theword nitrate insert with; column 8 hne 49, for on the read in the;column 10, line 57 under the headmg O'l HER REFERENCES, add Pichler,Bren/netoffe-d'hemie, 1.9, N o. 12, pages 226-230 (1938) and that thesaid Letters Patent should be read as corrected above, so that the samemay conform to the record of the case in the Patent Oifice.

Signed and sealed the 10th day of July, A. D. 1951.

ERNEST F. KLINGE,

Assistant Uonvmz'aaioncr of Patents.

1. A PROCESS FOR THE PREPARATION OF A RESINOUS OXYGEN-CONTAININGMATERIAL FROM A POLYMER OF A CONJUGATED DIOLEFIN CONTAINING FROM 4 TO 6CARBON ATOMS IN THE MOLECULE, HAVING A VISCOSITY WITHIN THE LIMITS OF200 AND 11,000 SUS AS MEASURED AT 100* F. AND HAVING A MOLECULAR WEIGHTWITHIN THE LIMITS OF 200 AND 2,000, COMPRISING REACTING SUCH A POLYMERWITH HYDROGEN AND CARBON MONOXIDE IN THE PRESENCE OF A CATALYST ACTIVEIN THE HYDROGENATION OF CARBON MONOXIDE WITH HYDROGEN FOR A CONTACT TIMEOF AT LEAST 100 MINUTES, AT A TEMPERATURE WITHIN THE LIMITS OF 100 AND400* F., AND AT A PRESSURE WITHIN THE LIMITS OF 50 AND 4500 P. S. I.,AND RECOVERING A RESINOUS OXYGEN-CONTAINING MATERIAL FROM THE REACTIONMIXTURE AS A PRODUCT OF THE PROCESS.